US4595639A - Radiographic intensifying screen - Google Patents

Radiographic intensifying screen Download PDF

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Publication number
US4595639A
US4595639A US06/647,885 US64788584A US4595639A US 4595639 A US4595639 A US 4595639A US 64788584 A US64788584 A US 64788584A US 4595639 A US4595639 A US 4595639A
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US
United States
Prior art keywords
sub
phosphor
intensifying screen
rare earth
activator
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US06/647,885
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English (en)
Inventor
Etsuo Shimizu
Yuji Aoki
Yujiro Suzuki
Norio Miura
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Kasei Optonix Ltd
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Kasei Optonix Ltd
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Filing date
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Priority claimed from JP58165055A external-priority patent/JPS6058482A/ja
Priority claimed from JP58169357A external-priority patent/JPS6063273A/ja
Application filed by Kasei Optonix Ltd filed Critical Kasei Optonix Ltd
Assigned to KASEI OPTONIX, LTD. reassignment KASEI OPTONIX, LTD. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: AOKI, YUJI, MIURA, NORIO, SHIMIZU, ETSUO, SUZUKI, YUJIRO
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes
    • G03C5/17—X-ray, infrared, or ultraviolet ray processes using screens to intensify X-ray images
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21K—TECHNIQUES FOR HANDLING PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
    • G21K4/00—Conversion screens for the conversion of the spatial distribution of X-rays or particle radiation into visible images, e.g. fluoroscopic screens
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7767—Chalcogenides
    • C09K11/7769—Oxides
    • C09K11/7771—Oxysulfides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating

Definitions

  • the present invention relates to a radiographic intensifying screen (hereinafter referred to simply as "intensifying screen”). More particularly, it relates to an intensifying screen having excellent image quality, particularly superior granularity.
  • the intensifying screen is used to fit on an X-ray film to improve the speed in a photographic system in various fields including radiography for medical purposes such as X-ray radiography used for medical diagnosis or radiography for industrial purposes such as non-destructive inspection of materials.
  • the intensifying screen comprises a support such as a paper or plastic sheet, and a fluorescent layer formed on one side of the support.
  • the fluorescent layer is composed of a binder resin and a phosphor dispersed in the binder and is capable of emitting high luminance light when irradiated by the radiation.
  • the surface of the fluorescent layer is usually protected by a thin transparent protective film such as a nitrocellulose film, a polymethacrylate film or a polyethylene terephthalate film.
  • intensifying screens wherein a rare earth oxysulfide phosphor containing terbium as an activator (hereinafter referred to simply as "rare earth oxysulfide phosphor") is used as the fluorescent layer, have been widely used as high speed intensifying screens.
  • the intensifying screens are desired to have a high sensitivity to radiation (i.e. a high light conversion efficiency or a high photographic speed) and good image quality such as low granularity and high sharpness.
  • the intensifying screens wherein a rare earth oxysulfide phosphor is used as the fluorescent layer have a substantially improved speed over the intensifying screens wherein the CaWO 4 phosphor is employed.
  • an improvement has been desired in this respect.
  • the present invention has been accomplished under these circumstances. It is an object of the present invention to improve the granularity of the conventional intensifying screen wherein a rare earth oxysulfide phosphor is used as a fluorescent layer and to provide an intensifying screen having a reduced after glow.
  • the above object can be accomplished by employing a rare earth oxysulfide phosphor co-activated by a first co-activator (R) composed of terbium (Tb) plus neodymium (Nd) and/or holmium (Ho), and, if necessary, further co-activated by a second co-activator (A) composed of at least one element selected from the group consisting of praseodymium (Pr), erbium (Er) and ytterbium (Yb).
  • R first co-activator
  • Tb terbium
  • Nd neodymium
  • Ho holmium
  • A second co-activator
  • the present invention has been accomplished based on this discovery.
  • the present invention provides a radiographic intensifying screen comprising a support and a fluorescent layer formed on the support, characterized in that said fluorescent layer is composed essentially of a rare earth oxysulfide phosphor represented by the formula:
  • Ln is at least one element selected from the group consisting of La, Gd, Y and Lu
  • R is at least one element selected from the group consisting of Nd and Ho
  • A is at least one element selected from the group consisting of Pr, Er and Yb
  • X, Y and Z are numbers within the ranges of 0.001 ⁇ x ⁇ 0.02, 0.0001 ⁇ y ⁇ 0.01 and O ⁇ z ⁇ 0.01, respectively, and x ⁇ y+z.
  • the intensifying screen of the present invention presents a remarkable improvement in the granularity, a substantial reduction of the after glow and little reduction of the sharpness, and it has a substantially higher speed than the conventional intensifying screen wherein the CaWO 4 phosphor is employed.
  • the granularity of the intensifying screen is substantially improved over the intensifying screen wherein a rare earth oxysulfide phosphor activated by terbium only is used.
  • the granularity of the intensifying screen can further be improved when a rare earth oxysulfide phosphor co-activated by the second co-activator (A) together with the first co-activator (R) is used.
  • FIGS. 1 (A), (B) and (C) are graphs showing the granularity characteristics of the intensifying screens of the present invention.
  • FIGS. 2 (A), (B) and (C) are graphs showing the sharpness characteristics of the intensifying screens of the present invention.
  • FIGS. 3 (A) and (B) are graphs showing the after glow characteristics of the intensifying screens of the present invention.
  • the intensifying screen of the present invention is produced substantially in the same manner as the production of the conventional intensifying screens except that the rare earth oxysulfide phosphor represented by the formula (Ln 1-x-y-z , Tb x , R y , A z ) 2 O 2 S is used for the fluorescent layer. Namely, proper amounts of the (Ln 1-x-y-z , Tb x , R y , A z ) 2 O 2 S phosphor and a binder resin such as nitrocellulose are mixed, and a proper amount of a solvent is further added to obtain a coating dispersion of the phosphor having an optimum viscosity.
  • the rare earth oxysulfide phosphor represented by the formula (Ln 1-x-y-z , Tb x , R y , A z ) 2 O 2 S is used for the fluorescent layer. Namely, proper amounts of the (Ln 1-x-y-z , Tb x , R y ,
  • This coating dispersion is applied onto a support by means of a roll coater or a knife coater and dried to form a fluorescent layer.
  • Some of intensifying screens have a structure in which a reflective layer such as a white pigment layer, a light absorptive layer such as a black pigment layer or a metal foil layer is interposed between the fluorescent layer and the support.
  • the reflective layer, light absorptive layer or metal foil layer may be preliminarily formed on the support as the case requires, and then a fluorescent layer composed of the (Ln 1-x-y-z , Tb x , R y , A z ) 2 O 2 S phosphor may be formed in the above-mentioned manner.
  • a protective coating dispersion prepared by adding a proper amount of a solvent to a resin such as polyvinyl chloride, polyethylene, cellulose acetate or polyacrylate to have the optimum viscosity, is applied on the previously formed fluorescent layer and dried to form a transparent protective film, as the case requires. Otherwise, it is also possible to prepare the fluorescent layer and the transparent protective film separately and then laminate and bond the fluorescent layer and the protective film onto a support in this order.
  • the granularity and the sharpness of an intensifying screen are mutually conflicting properties. Namely, when the granularity is improved, the sharpness tends to decrease.
  • the coating weight of the fluorescent layer is preferably from 10 to 100 mg/cm 2 in the dried state.
  • a light absorptive layer such as a black pigment layer between the support and the fluorescent layer.
  • a protective film is formed on the fluorescent layer, its thickness is preferably from 3 to 15 ⁇ m, more preferably from 3 to 10 ⁇ m.
  • FIG. 1 (B) and (C) illustrate the relationship between the total amount (y+z) of the content (y) of the first co-activator (R) and the content (z) of the second co-activator (A) in rare earth oxysulfide phosphors [(Ln 1-x-y-z , Tb x , R y , A z ) 2 O 2 S] used as fluorescent layers in the intensifying screens of the present invention, and the granularity of the intensifying screens using the phosphors. They represent the results of the measurements conducted with the photographic speed of the respective intensifying screens fixed at a predetermined level. Curves a, b and c in FIG.
  • the ordinate represents the granularity index number (G) and the abscissa represents the content (y) of the first co-activator (R) contained in the respective rare earth oxysulfide phosphors.
  • the ordinate represents the granularity index number (G) and the abscissa represents the total amount (y+z) of the contents of the first and second co-activators (R) and (A) contained in the respective rare earth oxysulfide phosphors.
  • the granularity index number (G) is a value represented by the following formula: ##EQU1## where [RMS(0)] is a RMS value of the conventional intensifying screen wherein a rare earth oxysulfide phosphor [(Gd 0 .99, Tb 0 .01) 2 O 2 S] containing no co-activator is used, and [RMS(yz)] is a RMS value of the intensifying screen of the present invention using the rare earth oxysulfide phosphor [(Gd 0 .99-y-z, Tb 0 .01, R y , A z ) 2 O 2 S] containing the co-activator (R) or co-activators (R) and (A) and having the same photographic speed (i.e.
  • RMS values at a photographic density of 1.0 and a spatial frequency of from 0.5 to 5 lines/mm The smaller, the RMS value, the better the granularity. Accordingly, the greater the value of the granularity index number (G), the better the granularity over the conventional intensifying screens using rare earth oxysulfide phosphors containing no co-activator. As is evident from FIGS. 1 (A), (B) and (C), by the addition of the co-activator (R) or co-activators (R) and (A) to the rare earth oxysulfide phosphor to be used for the fluorescent layer, the granularity of the intensifying screen thereby obtained is improved.
  • the ordinate represents the sharpness index number (M) and the abscissa represents the content (y) of the co-activator (R) contained in the respective rare earth oxysulfide phosphors to be used in the respective intensifying screens.
  • the ordinate represents the sharpness index number (M) and the abscissa represents the total amount (y+z) of the contents of the first and second co-activators (R) and (A) contained in the respective rare earth oxysulfide phosphors to be used in the respective intensifying screens.
  • the sharpness index number (M) is a value represented by the following formula: ##EQU2## where [MTF(0)] is a MTF value of a conventional intensifying screen using a rare earth oxysulfide phosphor [(Gd 0 .99, Tb 0 .01) 2 O 2 S] containing no co-activator, and [MTF (yz)] is a MTF value of an intensifying screen of the present invention using a rare earth oxysulfide phosphor [(Gd 0 .99-y-z, Tb 0 .01, R y , A z ) 2 O 2 S] containing the co-activator (R) or co-activators (R) and (A) and with the same photographic speed (i.e.
  • the sharpness index number (M) the sharpness of the intensifying screens using rare earth oxysulfide phosphors containing the co-activator (R) or co-activators (R) and (A) gradually lowers as the amount (y) of the first co-activator (R) or the total amount (y+z) of the first and second co-activators (R) and (A) increases.
  • the reduction of the sharpness is extremely small.
  • FIG. 3 (B) illustrates the relationship between the total amount (y+z) of the first and second co-activators (R) and (A) and the after glow characteristic of the intensifying screen using this phosphor. They represent the results of the measurements conducted with the photographic speed of the respective intensifying screens fixed at a predetermined level. Curves a, b and c in FIGS.
  • the quantity of light of the after glow of each intensifying screen was obtained as a relative value by irradiating X-rays to each intensifying screen under the same condition and after 1 second, fixing the intensifying screen on a X-ray film in a dark place, maintaining them for 30 minutes and then measuring the degree of blackness of the X-ray film.
  • the ordinate represents the after glow index number (L) and the abscissa represents the content (y) of the co-activator (R) in the rare earth oxysulfide phosphor.
  • the ordinate represents the after flow index number (L) and the abscissa represents the total amount (y+z) of the first and second co-activators (R) and (A) in the respective rare earth oxysulfide phosphors.
  • the after glow index number (L) is a value represented by the following formula: ##EQU3## where [L(0)] is the quantity of light of the after flow of a conventional intensifying screen using a rare earth oxysulfide phosphor [(Gd 0 .99, Tb 0 .01) 2 O 2 S] containing no co-activator, and [L(yz)] is the quantity of light of the after flow of an intensifying screen of the present invention using a rare earth oxysulfide phosphor containing the co-activator (R) or co-activators (R) and (A) and with the same photographic speed.
  • the after glow of the intensifying screen can remarkably be decreased as compared with the conventional intensifying screen using a rare earth oxysulfide phosphor containing no co-activator.
  • the rare earth oxysulfide phosphors of the present invention likewise provide intensifying screens having substantially the same granularity, sharpness and after glow characteristics as in the case of the illustrated rare earth oxysulfide phosphors.
  • the Tb content (x) in the rare earth oxysulfide phosphor of the formula (Ln 1-x-y-z , Tb x , R y , A z ) 2 O 2 S to be used as the fluorescent layer is preferably within a range of 0.001 ⁇ x ⁇ 0.02 from the viewpoint of the speed as in the case of the conventional rare earth oxysulfide phosphor containing no co-activator. Further, as is evident from FIGS.
  • the photographic speed of the intensifying screen thereby obtained will be substantially decreased.
  • the amount (y) of the co-activator (R) or the total content (y+z) of the co-activators (R) and (A) should preferably be at most the content (x) of the activator (Tb) i.e. x ⁇ y+z.
  • the intensifying screens of the present invention exhibit remarkably higher speeds than the conventional intensifying screens wherein CaWO 4 phosphor is employed. Further, the granularity can substantially be improved with a minimum decrease of the sharpness as compared with the conventional high speed intensifying screens wherein a rare earth oxysulfide phosphor activated by terbium only. Furthermore, the after glow can be reduced as compared with the conventional intensifying screens.
  • the present invention provides high speed intensifying screens which are capable of improving the diagnostic capability and which are thus quite useful for the industrial application.
  • Intensifying screens (1) to (25) were prepared in the following manner with use of the respective rare earth oxysulfide phosphors identified in Table 1.
  • a coating dispersion of the phosphor Eight parts by weight of the rare earth oxysulfide phosphor, 1 part by weight of nitrocellulose and an organic solvent were mixed to obtain a coating dispersion of the phosphor.
  • This coating dispersion of the phosphor was uniformly coated by means of a knife coater, on a polyethylene terephthalate support provided on its surface with an absorptive layer of carbon black so that the coating weight of the phosphor became as shown in Table 1, and dried to obtain a fluorescent layer.
  • a protective film-forming coating solution prepared by dissolving cellulose acetate in a solvent, was uniformly applied onto the surface of the fluorescent layer so that the film thickness after drying would be about 5 ⁇ m, and then dried to form a transparent protective film.
  • an intensifying screen STD was prepared in the same manner as above except that the rare earth oxysulfide phosphor identified by STD in Table 1 was used in the coating amount likewise identified in Table 1.
  • the intensifying screen (2) and the intensifying screen (16) or (17), or the comparison between the intensifying screen (6) and intensifying screen (19), (20) or (21), with respect to the intensifying screens using rare earth oxysulfide phosphors wherein the first co-activator (R) is the same if the speed of the intensifying screens is substantially the same, the intensifying screens using the rare earth oxysulfide phosphors containing the second co-activator (A) are superior in the granularity to the intensifying screens using the rare earth oxysulfide phosphors containing the first co-activator (R) only.
  • the characteristics of the respective intensifying screens are the speed, granularity index number (G) and sharpness index number (M) obtained by radiography conducted with X-rays generated at an X-ray tube voltage of 80 KV and passed through a water-phantom having a thickness of 8 cm by means of an ortho-film (RX-OG, manufactured by Fuji Photo Film Co. Ltd.).
  • G speed, granularity index number
  • M sharpness index number
  • Speed A relative value based on the speed of the intensifying screen (STD) having a fluorescent layer composed of (Gd 0 .99, Tb 0 .01) 2 O 2 S phosphor where its speed is set at 100.
  • Granularity index number (G) and sharpness index number (M) are as defined above, respectively.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Luminescent Compositions (AREA)
  • Conversion Of X-Rays Into Visible Images (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US06/647,885 1983-09-09 1984-09-06 Radiographic intensifying screen Expired - Fee Related US4595639A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP58165055A JPS6058482A (ja) 1983-09-09 1983-09-09 放射線増感紙
JP58-165055 1983-09-09
JP58-169357 1983-09-16
JP58169357A JPS6063273A (ja) 1983-09-16 1983-09-16 放射線増感紙

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US4595639A true US4595639A (en) 1986-06-17

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US (1) US4595639A (fr)
EP (1) EP0139192B1 (fr)
KR (1) KR910004840B1 (fr)
AU (1) AU560994B2 (fr)
CA (1) CA1256746A (fr)
DE (1) DE3466998D1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2614688C2 (ru) * 2015-05-18 2017-03-28 Общество с ограниченной ответственностью научно-производственная фирма "ЛЮМ" ЛЮМИНОФОР КОМПЛЕКСНОГО ПРИНЦИПА ДЕЙСТВИЯ НА ОСНОВЕ ОКСИСУЛЬФИДОВ РЕДКОЗЕМЕЛЬНЫХ ЭЛЕМЕНТОВ, АКТИВИРОВАННЫЙ ИОНАМИ Ho3+ И Yb3+

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0299409B1 (fr) * 1987-07-16 1992-09-30 Kasei Optonix, Ltd. Ecran radiographique renforçateur
DE10113267B4 (de) * 2001-03-16 2019-05-09 Bundesdruckerei Gmbh Verwendung eines Anti-Stokes-Leuchtstoffes in Sicherheitsdokumenten
EP2318476B1 (fr) * 2008-07-23 2018-01-03 Koninklijke Philips N.V. Matériau à base de gd2o2s destiné à être utilisé dans des applications de tomographie assistée par ordinateur (ct)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4486486A (en) * 1982-03-15 1984-12-04 Kasei Optonix, Ltd. Radiographic image conversion screens

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL7004337A (fr) * 1970-03-25 1971-09-28
US3856698A (en) * 1972-06-16 1974-12-24 Gen Electric Preparation of rare-earth oxysulfide luminescent material
US3850837A (en) * 1972-08-11 1974-11-26 Gen Electric Preparation of rare-earth oxysulfide luminescent material
US3878119A (en) * 1972-12-26 1975-04-15 Gen Electric Preparation of rare-earth oxysulfide phosphors
FR2464983A1 (fr) * 1979-09-07 1981-03-20 Anvar Procede de preparation de couches luminescentes d'oxysulfures de terres rares ou d'yttrium actives, moyen pour sa mise en oeuvre et materiaux obtenus

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4486486A (en) * 1982-03-15 1984-12-04 Kasei Optonix, Ltd. Radiographic image conversion screens

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2614688C2 (ru) * 2015-05-18 2017-03-28 Общество с ограниченной ответственностью научно-производственная фирма "ЛЮМ" ЛЮМИНОФОР КОМПЛЕКСНОГО ПРИНЦИПА ДЕЙСТВИЯ НА ОСНОВЕ ОКСИСУЛЬФИДОВ РЕДКОЗЕМЕЛЬНЫХ ЭЛЕМЕНТОВ, АКТИВИРОВАННЫЙ ИОНАМИ Ho3+ И Yb3+

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Publication number Publication date
AU560994B2 (en) 1987-04-30
EP0139192A2 (fr) 1985-05-02
AU3275184A (en) 1985-03-14
KR910004840B1 (ko) 1991-07-13
EP0139192B1 (fr) 1987-10-28
DE3466998D1 (en) 1987-12-03
KR850002121A (ko) 1985-05-06
EP0139192A3 (en) 1985-09-11
CA1256746A (fr) 1989-07-04

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